Quality Assurance Project Plan 

for the Chlorine and 

Chlorinated Hydrocarbons 

Sampling Program 

2007 Addendum 

Prepared for: 

U.S. Environmental Protection Agency 

Engineering and Analysis Division 

Office of Water 

1200 Pennsylvania Avenue, NW 

Washington, DC 20460 

Prepared by:

Eastern Research Group, Inc.

14555 Avion Parkway 

Suite 200 

Chantilly, VA 20151-1102 

July 9, 2007 

EPA Contract No. 68-C2-095 

Work Assignment 4-18 

ADDENDUM 

July 2007 

Page 1 of 7 

This addendum describes changes to the Final Quality Assurance Project Plan for 

the Chlorine and Chlorinated Hydrocarbon Sampling Program (Sampling QAPP) dated May 4, 

2006 for the 2006 CCH sampling program as well as changes that will be implemented for the 

2007 CCH sampling program. ERG followed most of the May 2006 plan for the 2006 CCH 

sampling program. However, based on the results of the initial 2006 data collection activities 

(not including the results for Episode 6540), ERG is amending Section 3.5 (Quality Control) as 

described in this addendum. All other sections of the Sampling QAPP remained unchanged. 

Changes Made for the 2006 CCH Sampling

 Bottle field blanks were collected in the staging area on Day 2 of the sampling 

episodes instead of prior to any sample collection, as specified in the May 4, 2006 version of the 

CCH QAPP. This change was made to collect data on potential contamination in the staging 

area during the sampling event, rather than before it began. 

Changes Planned for the 2007 CCH Sampling

Element B.4: Analytical Methods 

 Table 1 at the end of this document lists the analytical methods to be used to 

characterize CCH waste stream samples. The table lists the methods specified for the 2006 

sampling, the method used at the laboratory, the method update rule (MUR) method, and the 

method that will be used for the 2007 sampling. 

Element B.5: Quality Control 

 The CCH sampling program will include the collection of field quality control 

samples. The site-specific sampling plans will specify the quantities and types of blanks and 
ADDENDUM 

July 2007 

Page 2 of 7 

duplicate samples to be collected during each episode. EPA is amending the methodology used 

for the following quality control samples: 

 Trip blanks; 

 Equipment field blanks; 

 Bottle field blanks; and, 

 Source water. 

This addendum does not change the procedures used for the bottle blank or duplicates. ERG’s 

bottle blank (only one required for the entire CCH sampling program) was analyzed for dioxins 

and furans and PCBs during the 2006 sampling program and no pollutants were detected. This 

indicates that contamination from sampling equipment (bottles) is not likely. 

 

Trip Blanks 

 ERG prepares one trip blank for each sampling episode. The laboratories 

typically analyze these samples only for volatile organic compounds. However, EPA elected to 

have the laboratories also test for dioxins and PCBs for the 2006 CCH sampling program since 

these compounds are of particular interest to the CCH program. Based on the initial sampling 

results which did not detect volatile organics, dioxins and furans, or PCBs, EPA believes that 

sample transport, handling, and storage are not likely to cause sample contamination. For the 

2007 CCH sampling program, trip blanks will be analyzed for volatile organic compounds only. 

 Purpose: To monitor volatile organic contamination of samples 

during transport, field handling, and storage. 

 Recommended One trip blank per episode for volatile organic compounds. 

 Frequency: 
ADDENDUM 

July 2007 

Page 3 of 7 

The sampling crew will prepare a trip blank in ERG’s sample room before the start of the 

sampling episode by pouring an analyte-free matrix (typically HPLC water) into the sample 

bottles. ERG will preserve the samples and transport them unopened to the facility. Trip blanks 

are stored at the sampling staging area throughout the sampling episode. The sampling crew 

will place the samples on ice during the last day of sampling and ship the samples unopened to 

the laboratory. 

Equipment Field Blanks 

 As specified in the May 2006 Sampling QAPP, the sampling crew will collect 

equipment field blanks for all sampling techniques used by the sampling staff and for any special 

equipment used during the sample collection, such as cooling coils, ISCO composite samplers, 

tubing, funnels, etc. The equipment field blank evaluates any contamination of the sample from 

either the equipment used or ambient conditions at the site. During the 2006 CCH sampling 

program, ERG used cooling coils, composite containers, and funnels to collect the samples. The 

cooling coils are typically used only for the collection of volatile organic samples. The 

composite containers and funnels are used for the collection of Group I, Group II, BOD, and 

metals. The collection of dioxin/furan and PCBs typically use no equipment other than bottles 

because the lab composites the sample results. ERG plans to use the same sampling methods for 

the 2007 CCH sampling program. To collect field blanks, ERG pours HPLC water directly into 

sample bottles or composite containers at the sample point location. ERG uses the same 

technique for compositing, packing, and shipping the equipment field blank as for all other 

samples. 

 Generally, field blanks are analyzed only for trace metals. The CCH sampling 

program is not collecting trace metals samples but opted to collected field blanks for volatile and 

semivolatile organic compounds, dioxins and furans, and PCBs since we determined these 

parameters were most critical to the study. 
ADDENDUM 

July 2007 

Page 4 of 7 

 Based on the initial 2006 CCH sampling program results, EPA has reason to 

believe that sampling equipment and techniques and the sample point ambient conditions will 

not contaminate the samples with nonvolatile compounds. Indeed, results for the equipment 

field blanks in the 2006 CCH sampling program did not show any detects for dioxins and furans, 

volatile organics, or semivolatile organics. Only, one PCB congener was detected in one field 

equipment blank at a concentration less than one tenth of the minimum level. Thus, for the 2007 

CCH sampling program, EPA will only analyze equipment field blanks for volatile organics to 

verify that organic vapors present at the sampling site do not contaminate the sample. 

 Purpose: To monitor any contamination from sampling techniques 

(equipment used or ambient conditions). 

 Recommended: ERG will support EPA in determining the number of 

Frequency: equipment field blanks needed at each site. At least one 

 blank will be collected for each type of sampling technique 

or special equipment used. Equipment field blanks will be 

collected for volatile organic compounds. 

Bottle Field Blanks 

 During the 2006 CCH Sampling, ERG collected bottle field blanks at the 

sampling staging area at each site to determine if sampling activities conducted at the sampling 

staging area contribute volatile and semivolatile organic compounds, total metals, dioxins and 

furans, and PCBs to the sample. 

 The CCH sampling program is not collecting trace metals samples and is 

collecting bottle field blanks for volatile and semivolatile organic compounds, total metals, 

dioxins and furans, and PCBs since we determined these parameters were most critical to the 

study. 
ADDENDUM 

July 2007 

Page 5 of 7 

 Based on the initial 2006 CCH sampling program results, EPA has reason to 

believe that the staging area ambient conditions will not contaminate the samples and thus do not 

need to be measured for quality control. Indeed, initial results for the bottle field blanks in the 

2006 CCH sampling program did not show any detects for dioxins and furans, or semivolatile 

organics. Only sodium (metal) and acetone (a common lab contaminant) were detected. Both 

compounds were detected at concentrations less than ten times the minimum level. Thus, for the 

2007 CCH sampling program, ERG will not collect bottle field blanks. Instead, ERG will collect 

only equipment field blanks to evaluate contamination from ambient conditions at the sample 

points. 

Source Water 

 The ERG sampling crew will collect a grab sample of the source water used in 

CCH operations prior to its use to monitor for contaminants in the source water. During the 

2006 CCH sampling program, source water samples were monitored for all analytes except 

HEM/SGT-HEM. Since most CCH sites use treated river water as their process water, EPA 

expects some contaminants to be present in source water. However, sites would need to remove 

any contaminants prior to treatment regardless of the source of contamination. Some facility 

personnel have stated that the source water may be contributing to their overall dioxin loads. 

Thus, for the 2007 CCH sampling program, the source water will be analyzed for dioxins and 

furans only to evaluate source water as a potential source of dioxins. 
Table 1. Analytical Methods Used in the CCH Sampling Program 

Analyte 

Method Specified in 

CCH Sampling 

Plans for Episodes 

6531, 6532, and 

6540 

Method Used at 

Laboratory for 

6531 and 6532 

Method Update 

Rule Methoda 

Method Specified 

for 2007 CCH 

Sampling A

Total Suspended Solids (TSS) 

160.2 160.2 160.2 

Total Dissolved Solids (TDS) 

160.1 160.1 160.1 

Sulfate 300.1, Rev 2.1 300.0, Rev 2.1 300.0, Rev 2.1 300.0 Rev 2.1 Chloride 300.1, Rev 2.1 300.0, Rev 2.1 300.0, Rev 2.1 300.0, Rev 2.1 Alkalinity SM2320B SM2320B SM2320B SM2320B Total Kjeldahl Nitrogen (TKN) 

SM4500-Norg B or 

C 

351.2 SM4500-Norg B or 

C 

351.1, 351.2,

SM4500-Norg B or 

C 

Ammonia SM4500-NH3 B,F SM 4500-NH3 B,G SM4500-NH3 B,F SM4500-NH3 B,F EPA’s SCC did not 

B, G on the deliver

Nitrate/Nitrite 300.1, Rev 2.1 353.2 300.0, Rev 2.1 300.0, Rev 2.1 EPA’s SCC inform

Laboratory Servicethe old analytical mhandle chloride intemethod listed on thRev 2.1. EPA appr

Phosphorus 365.2 or 365.4 365.1 365.3 or SM4500P 

B(5) E 

365.1, 365.3, 365.4 

or SM4500P B(5) E 

Biochemical Oxygen Demand (BOD) 

SM5210B SM5210B SM5210B SM5210B 

Chemical Oxygen Demand (COD) 

410.4, Rev 2 HACH 8000 410.4, Rev 2 410.4, Rev 2 or 

HACH 8000 
Table 1. (Continued) 

Analyte 

Method Specified in 

CCH Sampling 

Plans for Episodes 

6531, 6532, and 

6540 

Method Used at 

Laboratory for 

6531 and 6532 

Method Update 

Rule Methoda 

Method Specified 

for 2007 CCH 

Sampling A

Total Organic Carbon (TOC) 

SM5310C SM5310B SM5310C SM5310B or 

SM5310C 

Hexane Extractable Material (HEM) and Silica Gel TreatedHexane Extractable Material (SGT-HEM) 

1664A 1664A 1664A 

Metals 200.7, 200.8, 200.9 200.7, 200.8, 200.9 200.7, 200.8, 200.9 200.7, 200.8, 200.9 CCH sampling also Volatile Organic Compounds (VOC) 

1624C 1624C 1624C 1624C 

Semivolatile Organic Compounds 

1625C 1625C 1625C 1625C 

Chlorinated Biphenyls Congeners (PCBs) 

1668A 1668A 1668A 1668A CCH is not pH pres

EPA and EPA’s SC

Tetra- Through OctaChlorinated Dioxins and Furans (D/F) 

1613B 1613B 1613B 1613B 

a Based on information provided by CSC.